CN113351220B - CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 Preparation method and application of - Google Patents
CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 Preparation method and application of Download PDFInfo
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- CN113351220B CN113351220B CN202110544866.9A CN202110544866A CN113351220B CN 113351220 B CN113351220 B CN 113351220B CN 202110544866 A CN202110544866 A CN 202110544866A CN 113351220 B CN113351220 B CN 113351220B
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- 229910003336 CuNi Inorganic materials 0.000 title claims abstract description 151
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 40
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 88
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 44
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 44
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 44
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 claims abstract description 42
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- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 claims description 61
- 229930182837 (R)-adrenaline Natural products 0.000 claims description 56
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- 238000001514 detection method Methods 0.000 claims description 45
- 108010029541 Laccase Proteins 0.000 claims description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 29
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 claims description 28
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 22
- 238000002835 absorbance Methods 0.000 claims description 20
- UCTWMZQNUQWSLP-UHFFFAOYSA-N adrenaline Chemical compound CNCC(O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003344 environmental pollutant Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
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- MIIIXQJBDGSIKL-UHFFFAOYSA-N 2-morpholin-4-ylethanesulfonic acid;hydrate Chemical compound O.OS(=O)(=O)CCN1CCOCC1 MIIIXQJBDGSIKL-UHFFFAOYSA-N 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
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- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 7
- 238000011088 calibration curve Methods 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 claims description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 5
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 4
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 claims description 4
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 3
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- 230000035484 reaction time Effects 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 229910018864 CoMoO4 Inorganic materials 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims description 2
- HNGDOSBFYRVIEY-UHFFFAOYSA-N ethanesulfonic acid;hydrate Chemical compound O.CCS(O)(=O)=O HNGDOSBFYRVIEY-UHFFFAOYSA-N 0.000 claims description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
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- LVNMAAGSAUGNIC-BQBZGAKWSA-N Cys-His Chemical compound SC[C@H](N)C(=O)N[C@H](C(O)=O)CC1=CNC=N1 LVNMAAGSAUGNIC-BQBZGAKWSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- 229910020598 Co Fe Inorganic materials 0.000 description 1
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
The invention relates to CuNi/CoMoO serving as a multifunctional laccase-like enzyme 4 The preparation method and the application thereof comprise the following steps: s1: CoMoO 4 Preparation of (a) and S2: CuNi/CoMoO 4 And (4) preparing. The invention adopts a method combining hydrothermal treatment, calcination and impregnation to prepare CuNi/CoMoO 4 Is favorable for adsorbing reactants to participate in enzyme catalytic reaction and shows better catalytic activity. Using CuNi/CoMoO 4 The ascorbic acid colorimetric sensor is established by the laccase-like activity, a portable intelligent terminal platform combined with a chrominance signal is established, and efficient degradation of acid fuchsin is realized.
Description
Technical Field
The invention relates to a chemical substance preparation and determination technology, in particular to CuNi/CoMoO serving as a multifunctional laccase-like enzyme 4 The preparation method and the application thereof.
Background
The nano material with the biological enzyme-like activity is called nano enzyme, and because the nano material can overcome the defects of long fermentation time, low yield, poor stability and the like inherent in natural enzyme, the nano material draws great attention and interest in various fields. At present, a plurality of nano enzymes are proved to have peroxidase, oxidase and hydrogen peroxideEnzyme, superoxide dismutase and laccase, and has wide application prospect in biosensing, pollutant degradation and environment restoration. For example, MMoO has been successfully prepared 4 (M ═ Co, Ni) nanoflower having peroxidase-like activity and useful for copper ion (Cu) 2+ ) Selective detection of (2). Metal Organic Framework (MOF) derived Co has also been prepared 3 O 4 The @ Co-Fe oxide double-shell nanocage is used as a multifunctional specific peroxidase-like nanoenzyme catalyst, a multifunctional platform for detecting acetylcholinesterase is constructed, the activity of Peroxymonosulfate (PMS) can be well activated, and after 10 cycles, the degradation efficiency of Acid Fuchsin (AF) is still kept at 92.3%.
However, few laccase-like active nanoenzymes have been reported, compared to nanoenzymes with peroxidase-like activity. Natural laccase is a copper-containing polyphenol oxidase, which can directly convert O 2 Reduction to H 2 O without producing H 2 O 2 Widely distributed in bacterial, fungal and plant species. Recently, researchers have prepared a novel nano enzyme with laccase-like activity by coordination of Cu (I)/Cu (II) and cysteine (Cys) -histidine (His) dipeptide, and the nano enzyme is used for degrading and detecting phenolic pollutants by modifying active sites and electron transfer pathways.
However, the preparation of multifunctional nanoenzymes with high laccase-like activity for chemical and biological sensing, contaminant degradation, and PMS activation, etc. remains a great challenge. In recent years, mixed transition metal molybdate oxides have received increasing attention as a catalyst material with high catalytic activity. CoMoO with large specific surface area 4 Exhibit excellent catalytic activity in various fields such as catalysis, lithium ion batteries, high-performance supercapacitors and sensors. For example, a CoMoO having a large specific surface area is prepared by a simple hydrothermal method 4 Due to the synergistic effect of good oxidation-reduction property of Co element and good conductivity of Mo element, Co element shows higher peroxidase-like activity and is used for colorimetric detection of H 2 O 2 . Nickel as a rich and stable metalThe field of catalysis is widely studied, and some people prepare Ni/Cu nanosheet arrays through constant-current electrodeposition, and show high electrocatalytic activity on Hydrogen Evolution Reaction (HER). Some successfully prepare CuNi-NPs loaded MIL-101 nano composite material, have high catalytic activity and are used for aminoborane hydrolysis. In previous reports, the metal Cu and Ni nanoparticles have strong synergistic effect, and can improve the catalytic activity.
However, the preparation of multifunctional nanoenzymes with high laccase-like activity and the application thereof in chemical and biological sensing, pollutant degradation and other aspects are still technical problems to be solved in the field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides CuNi/CoMoO as a multifunctional laccase-like enzyme 4 The CuNi/CoMoO is prepared by a method combining hydrothermal, calcination and impregnation 4 The CuNi nano-particles increase the specific surface area of the composite material, expose more Cu (I) active centers, facilitate the adsorption of reactants to participate in enzyme catalytic reaction, and show better catalytic activity. The invention also provides a CuNi/CoMoO as a multifunctional laccase-like enzyme 4 Using CuNi/CoMoO 4 The activity of the laccase-like enzyme establishes a colorimetric sensor of ascorbic acid, can effectively degrade phenolic pollutants and environmental pollutants, takes epinephrine as a model of the phenolic pollutants, establishes a portable intelligent terminal platform combined with chrominance signals, realizes convenient, visual and intuitive detection, and realizes efficient degradation of acid fuchsin.
In order to achieve the purpose, the invention adopts the main technical scheme that:
CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 The preparation method comprises the following steps:
S1：CoMoO 4 preparation of
Mixing Na 2 MoO 4 ·2H 2 O and Co (NO) 3 ) 2 ·6H 2 O is fully stirred and dissolved in deionized water, and then the mixture is placed in an autoclaveIn the reaction; after centrifugal separation, washing with deionized water and ethanol for three times to obtain a precursor; then vacuum drying is carried out, and the precursor is calcined to obtain the CoMoO 4 ；
S2：CuNi/CoMoO 4 Preparation of
Adding CuCl 2 ·2H 2 O、NiCl 2 ·6H 2 O and prepared CoMoO 4 Dissolving in deionized water and stirring; then adding NaHB 4 Stirring, washing with deionized water and ethanol, and vacuum drying to obtain CuNi/CoMoO 4 。
Further, in step S1:
Na 2 MoO 4 ·2H 2 o and Co (NO) 3 ) 2 ·6H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1;
the reaction conditions in the autoclave were: the reaction temperature is 155-165 ℃, and the reaction time is 9-11 h;
the vacuum drying temperature is 75-85 ℃, the calcining temperature is 345-355 ℃, and the calcining time is 1.5-2.5 h.
Further, in step S2:
CuCl 2 ·2H 2 o and NiCl 2 ·6H 2 The dosage ratio of O is a molar ratio which is 1-6: 1;
stirring in deionized water for 2-4 h;
NaHB 4 the concentration of (A) is 9-11mgmL -1 Adding NaHB 4 The later stirring time is 4-6 h;
the temperature of vacuum drying is 75-85 ℃.
According to a second aspect of the invention, the CuNi/CoMoO obtained 4 Application to the determination of ascorbic acid:
uniformly dispersing CuNi/CoMoO 4 Adding into tris buffer solution, adding 2, 4-dichlorophenol, 4-aminoantipyrine and ascorbic acid with different concentrations, and incubating at 37 deg.C for 1.5h to obtain red sample;
then, measuring the absorbance of the reaction solution at 510nm by using an ultraviolet-visible spectrophotometer;
wherein the content of the first and second substances,
CuNi/CoMoO 4 the concentration of (3) is 1.0mg/mL, the pH of the tris hydrochloride buffer solution is 6.5, the concentration of 2, 4-dichlorophenol is 1mg/mL, and the concentration of 4-aminoantipyrine is 1 mg/mL.
Furthermore, the linear detection range of the ascorbic acid is 1-150 mu M, and the detection limit is 0.70 mu M;
wherein:
when the linear detection range of the ascorbic acid is 1-50 mu M, the calibration curve is that Y is 0.04281X +0.05396, R 2 ＝0.98826；
When the linear detection range of the ascorbic acid is 51-150 mu M, the calibration curve is that Y is 0.00616X +1.69368, R 2 ＝0.99611；
Wherein: and X is the concentration of ascorbic acid.
According to a third aspect of the invention, the CuNi/CoMoO obtained 4 The method is applied to the catalytic degradation of phenolic pollutants:
uniformly dispersing CuNi/CoMoO 4 Adding the mixture into 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution, then respectively adding different laccase substrates and 4-aminoantipyrine, incubating for 1.5h at 37 ℃, and then measuring the absorbance of different laccase substrates at 510nm by using an ultraviolet-visible spectrophotometer;
the laccase substrate is benzenediol, phenol, dichlorophen, parachlorophenol, o-nitrophenol or o-aminophenol;
wherein the content of the first and second substances,
CuNi/CoMoO 4 the concentration of (a) is 1.0mg/mL, the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer is 7.0, the concentration is 50mM, the concentration of the laccase substrate is 1mg/mL, and the concentration of the 4-aminoantipyrine is 1 mg/mL.
According to the fourth aspect of the invention, the prepared CuNi/CoMoO 4 Application to the catalytic degradation of acid fuchsin:
preparation of CuNi/CoMoO containing acid fuchsin solution and peroxymonosulfate 4 Mixing the suspension, uniformly dispersing with ultrasonic wave, and measuring suspension at 545nm with UV-visible spectrophotometerAbsorbance of the solution;
wherein the content of the first and second substances,
the pH of the acid fuchsin solution is 3.0-6.0, and the CuNi/CoMoO 4 Has a concentration of 1.5mg/mL and a concentration of peroxymonosulfate of 2mg/mL -1 。
According to a fifth aspect of the invention, the CuNi/CoMoO is prepared 4 Application to the catalytic oxidation of epinephrine:
different concentrations of epinephrine are injected into a solution containing CuNi/CoMoO 4 In 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution of the aqueous dispersion, the mixture is reacted for 1.5h at 37 ℃ for oxidation, and then the epinephrine oxidation product is measured at 485nm by an ultraviolet spectrophotometer;
wherein:
CuNi/CoMoO 4 the concentration of (A) is 1.0mg/mL, the pH of the 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution is 7.0, and the concentration is 50 mM;
the linear curve of epinephrine and absorbance is Y-0.01661X +0.12833, R 2 0.99745, X is the concentration of epinephrine, and the linear detection range of epinephrine is 5 to 50 μ g/mL.
According to the sixth aspect of the invention, the prepared CuNi/CoMoO is detected based on the visual detection platform of the portable intelligent terminal 4 Visual assay applied to epinephrine:
different concentrations of epinephrine were mixed with CuNi/CoMoO 4 Mixing and reacting for 1.5h in 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution at 37 ℃; then adding CuNi/CoMoO 4 Transferring the epinephrine mixed solution into a glass test tube, placing the test tube in a black box and illuminating with a fluorescent lamp;
then, an intelligent terminal is used for collecting colorimetric images, multiple regions of the obtained photos are selected and converted into R, G, B channel values, APP is used for fitting a reaction standard curve of epinephrine according to R/G, and finally the detection results of a linear equation and a correlation coefficient are displayed on a screen;
wherein:
CuNi/CoMoO 4 the concentration of (2) - (N-morpholino) ethanesulfonic acid monohydrate buffer solution is 1.0mg/mL, pHWas 7.0 at a concentration of 50 mM.
Further, the curve fitted with epinephrine is Y ═ 0.7561+0.0344X, R 2 And (3) 0.9937, wherein X is the concentration of adrenaline, and the linear detection range of the adrenaline is 5-50 mu g/mL.
The invention has the beneficial effects that:
(1) the CuNi/CoMoO is prepared by a method combining hydrothermal treatment, calcination and impregnation 4 The CuNi nano-particles increase the specific surface area of the composite material, expose more Cu (I) active centers, facilitate the adsorption of reactants to participate in enzyme catalytic reaction, and show better catalytic activity even under extreme pH, temperature, long-term storage and high salt concentration 4 Also shows higher activity.
(2) Using CuNi/CoMoO 4 The laccase-like enzyme activity establishes a colorimetric sensor of ascorbic acid, the linear range of the colorimetric sensor is 1-150 mu M, the detection limit is 0.70 mu M, and the detection limit and the linear range of the colorimetric sensor are equivalent to or even better than those of methods obtained by other sensors.
(3) Can effectively degrade phenolic pollutants and environmental pollutants, CuNi/CoMoO 4 Not only can catalyze the oxidation of phenolic substances, but also has catalytic activity equivalent to or slightly superior to laccase, and the catalytic activity shows that CuNi/CoMoO 4 The nano enzyme has good substrate universality.
(4) A portable intelligent terminal platform combined with a chrominance signal is constructed by taking epinephrine as a model of phenolic pollutants, and a visual, visual and convenient epinephrine instant detection method is established without expensive equipment.
(5)CuNi/CoMoO 4 Due to the catalytic generation of SO 4 ·- And OH, realizing efficient degradation of acid fuchsin.
Drawings
FIG. 1 shows CuNi/CoMoO 4 Schematic representation of laccase-like nanoenzyme catalysis mechanism.
FIG. 2 shows CuNi/CoMoO 4 Schematic synthesis of (a).
FIG. 3 is a CoMoO 4 Sweeping ofElectron Microscope (SEM) images were taken.
FIG. 4 is a schematic representation of CuNi/CoMoO 4 Scanning Electron Microscope (SEM) images of (a).
FIG. 5 is a schematic representation of CuNi/CoMoO 4 Transmission Electron Microscope (TEM) images of (a).
FIG. 6 is a schematic representation of CuNi/CoMoO 4 The ultraviolet absorption spectrum of (1) with or without Ascorbic Acid (AA).
FIG. 7 is a calibration curve for Ascorbic Acid (AA).
Fig. 8 is a graph of Total Antioxidant Capacity (TAC) measured in a commercial beverage using ascorbic acid as a model.
FIG. 9 is a schematic representation of CuNi/CoMoO 4 Comparing the catalytic effect of natural laccase on different phenolic substrates (n ═ 3), wherein a1 is CuNi/CoMoO 4 Catalyzing the absorbance of different phenolic substrates, and a2 is the absorbance of the natural laccase catalyzing different phenolic substrates.
FIG. 10 shows 2- (N-morpholino) ethanesulfonic acid monohydrate (PMS), CuNi/CoMoO 4 And CuNi/CoMoO 4 The effect of PMS system on Acid Fuchsin (AF) degradation is shown.
Figure 11 is the effect of initial pH on AF degradation.
FIG. 12 shows the reaction rate constants (k) for AF solutions at different pH values.
FIG. 13 is a schematic representation of CuNi/CoMoO 4 The method is applied to the relation between different concentrations of adrenalin (n-3) and absorbance.
FIG. 14 is a CuNi/CoMoO-based alloy 4 Schematic diagram of applying to visual analysis determination APP colorimetric signal quantitative determination adrenaline of adrenaline.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The technical scheme of the invention is summarized as follows: the invention provides a CuNi/CoMoO serving as a multifunctional laccase-like enzyme 4 The CuNi/CoMoO is prepared by a method combining hydrothermal, calcination and impregnation 4 More effective active sites, and the introduction of CuNi nano particles increases the ratio of the composite materialThe surface area exposes more Cu (I) active centers, which is beneficial to adsorbing reactants to participate in enzyme catalytic reaction and shows better catalytic activity. The invention also provides a CuNi/CoMoO as a multifunctional laccase-like enzyme 4 Using CuNi/CoMoO 4 The activity of the laccase-like enzyme establishes a colorimetric sensor of ascorbic acid, can effectively degrade phenolic pollutants and environmental pollutants, takes epinephrine as a model of the phenolic pollutants, establishes a portable intelligent terminal platform combined with chrominance signals, realizes convenient, visual and intuitive detection, and realizes efficient degradation of acid fuchsin. CuNi/CoMoO of the invention 4 The laccase-like nanoenzyme catalysis mechanism is shown in fig. 1.
To illustrate the solution and technical advancement of the present invention, the technical solution and technical application designed now are as follows:
CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 The preparation method comprises the following steps:
S1：CoMoO 4 preparation of
Mixing Na 2 MoO 4 ·2H 2 O and Co (NO) 3 ) 2 ·6H 2 Fully stirring and dissolving O in deionized water, and then reacting in a high-pressure kettle; after centrifugal separation, washing with deionized water and ethanol for three times to obtain a precursor; then vacuum drying is carried out, and the precursor is calcined to obtain CoMoO 4 ；
S2：CuNi/CoMoO 4 Preparation of
Adding CuCl 2 ·2H 2 O、NiCl 2 ·6H 2 O and prepared CoMoO 4 Dissolving in deionized water and stirring; then adding NaHB 4 Stirring, washing with deionized water and ethanol, and vacuum drying to obtain CuNi/CoMoO 4 。
In step S1: na (Na) 2 MoO 4 ·2H 2 O and Co (NO) 3 ) 2 ·6H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1; the reaction conditions in the autoclave were: the reaction temperature is 155-165 ℃, and the reaction time is 9-11 h; the vacuum drying temperature is 75-85 deg.C, and the calcining temperature isAt 345 ℃ and 355 ℃, the calcination time is 1.5-2.5 h.
In step S2: CuCl 2 ·2H 2 O and NiCl 2 ·6H 2 The dosage ratio of O is a molar ratio which is 1-6: 1; stirring in deionized water for 2-4 h; NaHB 4 The concentration of (A) is 9-11mg/mL, NaHB is added 4 The later stirring time is 4-6 h; the temperature for vacuum drying is 75-85 ℃.
The prepared CuNi/CoMoO 4 Application to the determination of ascorbic acid: uniformly dispersing CuNi/CoMoO 4 Adding into tris buffer solution, adding 2, 4-dichlorophenol, 4-aminoantipyrine and ascorbic acid with different concentrations, and incubating at 37 deg.C for 1.5h to obtain red sample; then, measuring the absorbance of the reaction solution at 510nm by using an ultraviolet-visible spectrophotometer; wherein, CuNi/CoMoO 4 The concentration of (2) is 1.0mg/mL, the pH of the tris hydrochloride buffer solution is 6.5, the concentration of 2, 4-dichlorophenol is 1mg/mL, and the concentration of 4-aminoantipyrine is 1 mg/mL.
The linear detection range of the ascorbic acid is 1-150 mu M, and the detection limit is 0.70 mu M; wherein: when the linear detection range of the ascorbic acid is 1-50 mu M, the calibration curve is that Y is 0.04281X +0.05396, R 2 0.98826; when the linear detection range of the ascorbic acid is 51-150 mu M, the calibration curve is that Y is 0.00616X +1.69368, R 2 0.99611; wherein: and X is the concentration of ascorbic acid.
The prepared CuNi/CoMoO 4 The method is applied to the catalytic degradation of phenolic pollutants: uniformly dispersing CuNi/CoMoO 4 Adding the mixture into 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution, then respectively adding different laccase substrates and 4-aminoantipyrine, incubating for 1.5h at 37 ℃, and then measuring the absorbance of different laccase substrates by using an ultraviolet-visible spectrophotometer; the laccase substrate is benzenediol, phenol, dichlorophen, parachlorophenol, o-nitrophenol or o-aminophenol; wherein, CuNi/CoMoO 4 The concentration of (a) is 1.0mg/mL, the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer is 7.0, the concentration is 50mM, the concentration of the laccase substrate is 1mg/mL, and the concentration of the 4-aminoantipyrine is 1 mg/mL.
The prepared CuNi/CoMoO 4 Application to the catalytic degradation of acid fuchsin: preparation of a solution containing acid fuchsin, peroxymonosulfate and CuNi/CoMoO 4 Uniformly dispersing the mixed solution of the suspension by using ultrasonic waves, and measuring the absorbance of the suspension at 545nm by using an ultraviolet-visible spectrophotometer; wherein the pH of the acid fuchsin solution is 3.0-6.0, and the pH value of the acid fuchsin solution is CuNi/CoMoO 4 The concentration of (2) is 1.5mg/mL and the concentration of peroxysulphate is 2 mg/mL.
The prepared CuNi/CoMoO 4 Application to the catalytic oxidation of epinephrine: different concentrations of epinephrine are injected into a solution containing CuNi/CoMoO 4 In 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution of the aqueous dispersion, the mixture is reacted for 1.5h at 37 ℃ for oxidation, and then the epinephrine oxidation product is measured at 485nm by an ultraviolet spectrophotometer; wherein: CuNi/CoMoO 4 The concentration of (A) is 1.0mg/mL, the pH of the 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution is 7.0, and the concentration is 50 mM; the linear curve of epinephrine and absorbance is Y-0.01661X +0.12833, R 2 0.99745, X is the concentration of epinephrine, and the linear detection range of epinephrine is 5 to 50 μ g/mL.
The prepared CuNi/CoMoO 4 Visual analytical assay applied to epinephrine: different concentrations of epinephrine were mixed with CuNi/CoMoO 4 Mixing and reacting for 1.5h in 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution at 37 ℃; then adding CuNi/CoMoO 4 Transferring the epinephrine mixed solution into a glass test tube, placing the test tube in a black box and illuminating with a fluorescent lamp; then, an intelligent terminal is used for collecting colorimetric images, multiple regions of the obtained photos are selected and converted into R, G, B channel values, APP is used for fitting a reaction standard curve of epinephrine according to R/G, and finally the detection results of a linear equation and a correlation coefficient are displayed on a screen; wherein: CuNi/CoMoO 4 The concentration of (3) was 1.0mg/mL, and the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer was 7.0 and the concentration was 50 mM.
The curve fitted for epinephrine is Y-0.7561 +0.0344X, R 2 0.9937, X is the concentration of epinephrine, and the linear detection range of epinephrine is5～50μg/mL。
Example (b):
(I) CuNi/CoMoO 4 Preparation examples
S1：CoMoO 4 Preparation of
Adding 1mmol Na 2 MoO4·2H 2 O and 1mmolCo (NO) 3 ) 2 ·6H 2 O is fully stirred and dissolved in 40mL deionized water, and then the mixture reacts in a 50mL autoclave at 160 ℃ for 10 hours; after centrifugal separation, washing with deionized water and ethanol for three times to obtain a precursor; then vacuum drying is carried out at 80 ℃, and the precursor is calcined for 2h under the air condition of 350 ℃ to obtain the CoMoO 4 。
S2：CuNi/CoMoO 4 Preparation of
The molar ratio of the components is 3: 0.0768g of CuCl were weighed out in 1 2 ·2H 2 O, 0.0387g of NiCl 2 ·6H 2 Ono and S1 prepared 0.04g of CoMoO 4 Dissolved in 20mL deionized water and stirred for 3h, then 10mL, 10mg/mL NaHB was added 4 Stirred for 5h, then washed with deionized water and ethanol and dried under vacuum at 80 ℃ to give a Cu/Ni molar ratio of about 3: 1 CuNi/CoMoO 4 。
As shown in FIGS. 1 to 4, CuNi/CoMoO is prepared by a combined hydrothermal, calcination and impregnation method 4 FIG. 1 shows CuNi/CoMoO 4 The synthesis process of (2); scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) images show the results from CoMoO 4 To CuNi/CoMoO 4 As shown in fig. 2-4. CoMoO 4 A rod-like structure and a smooth surface were exhibited (fig. 2). After CuNi nanoparticles (CuNi-NPs) are grown, in a CuNi/CoMoO 4 Medium, CoMoO 4 The rod-like structure of the body was maintained, but the surface was roughened and irregular by loading CuNi-NPs (fig. 3). The transmission electron microscope further proves that CuNi/CoMoO 4 A rod-like structure with a rough surface (fig. 4). The CuNi nano particles can be well dispersed in CoMoO with a rod-like structure 4 In addition, a more effective active site is provided for improving the laccase activity. The introduction of CuNi nano particles increases the specific surface area of the composite material, exposes more Cu (I) active centers and is beneficial to absorptionThe additional reactant participates in the enzyme catalytic reaction, and shows better catalytic activity.
CuNi/CoMoO 4 The catalysis mechanism of (2) is shown in figure 1, and the copper cluster is the main active center of the natural laccase catalytic oxidation-reduction reaction. Laccase can promote O by combining with substrate oxidation 2 Reduction of four electrons to H 2 O and can oxidize some environmental pollutants (e.g., phenol). Laccase, as a multicopper oxidase, is classified into type 1 (T1), type 2 (T2) and binuclear type 3 (T3) according to its unique spectral characteristics. The oxidation of the substrate by the natural laccase takes place in the vicinity of T1. Thereafter, electrons are transferred through the Cys-His pathway
The three-core copper cluster of T2/T3 is reached, and then redox occurs. According to previous reports, T1 is considered to be a metal-containing Electron Transfer (ET) active site, consisting of a short Cu-S (Cys) bond and two normal Cu-N (His) bonds. Cys-His is thought to be a bridge linking the remote catalytically active site to T1-Cu during electron transfer, and it contains two potential electron transfer pathways: pathway 1(P1) passes through the protein backbone and pathway 2(P2) passes through hydrogen bonds between Cys-His. Due to Cu + /Cu 0 Has a redox potential higher than that of Cu 2+ /Cu + Thus, the electron transfer from the Cys-His pathway in native laccases is from Cu + To Cu 2+ 。
In the presence of CuNi/CoMoO 4 In the catalysis of nano enzyme, 2, 4-dichlorophenol (2,4-DP) is used as a phenolic substrate, CuNi/CoMoO 4 Possible catalytic pathways are shown in figure 1. The catalytic pathway mainly comprises four processes: (i) substrate adsorption, (ii) substrate oxidation, (iii) electron transfer and (iv) O transfer by four electrons 2 Reduction to H 2 And O. Specifically, Cu (Cu) is bonded to Ni Ⅰ ) More active, phenolic substrates 2,4-DP are coated with CuNi/CoMoO 4 Cu of nanoenzyme Ⅰ And (4) adsorbing. Then, due to Cu Ⅰ Oxidation ability of (2) is higher than that of Cu II High, phenolic substrates by Cu Ⅰ Oxidation to phenolic hydroxyl radical with Cu Ⅰ Is reduced to Cu 0 . Subsequently, reduced Cu 0 Quilt O 2 Further oxidized to Cu Ⅰ ，O 2 As the primary acceptor site for single electron oxidation, electrons are transferred from Cu via steric interactions (saturation bonds, covalent bonds and hydrogen bonding electron transfer pathways) Ⅰ Transfer to Cu II . After obtaining electrons, Cu II Conversion to Cu Ⅰ . Cu in the reaction system due to lack of protection of chemical groups Ⅰ Quilt O 2 Oxidation to Cu II While being O 2 Is reduced to H by four electron transfer 2 And O. Finally CuNi/CoMoO 4 The nanoenzyme is recycled.
(II) CuNi/CoMoO 4 Analytical determination example applied to Ascorbic Acid (AA)
First, 100. mu.L of 1.0mg/mL of uniformly dispersed CuNi/CoMoO is added 4 Tris-HCl buffer (1.5 mL) at pH6.5 was added to 100. mu.L of 2, 4-dichlorophenol (1 mg/mL), 100. mu.L of 4-aminoantipyrine (4-AP) at a concentration of 1mg/mL and ascorbic acid (different concentrations) and incubated at 37 ℃ for 1.5h to form a red sample. The absorbance of the reaction solution was measured at 510nm with an ultraviolet-visible spectrophotometer.
Based on CuNi/CoMoO, as shown in FIGS. 6-8 4 The laccase-like activity of (2) establishes a simple colorimetric chemical/biosensor for detecting AA. Under the optimal conditions, at 37 ℃, pH6.5 (Tris-HCl buffer), the system reacts for 1.5h, and the mixture of 2, 4-dichlorophenol and 4-AP does not absorb at 510nm, as shown in figure 6, 2, 4-dichlorophenol, 4-AP and CuNi/CoMoO 4 The mixture of (1) has a strong absorption at 510 nm. However, after adding AA to the mixture, the absorbance at 510nm decreased dramatically as shown in fig. 6, demonstrating the feasibility of AA detection. The linear dynamic range and limit of detection were obtained by tracking the uv-vis absorbance at 510nm for a series of mixed solutions of different AA concentrations. Within the range of 1-150 μ M, the Δ A value of ascorbic acid is linear with concentration, as shown in FIG. 7. The limit of detection (LOD) for AA is based on 3 σ/b (where σ is the standard deviation of the blank signal and b is the slope of the regression line) (S/N-3) with an ultra-low limit of detection of 0.70 μ M. As shown in Table 1, the detection limits and linear range of the present invention and other sensingThe method obtained by the device is equivalent to or even better.
Table 1 analytical method comparison for ascorbic acid detection.
Determination of Total Oxidation resistance (TAC)
As shown in fig. 8, the total antioxidant capacity of 5 commercial beverages was measured using ascorbic acid as an antioxidant model. In the determination of total antioxidant capacity, the conditions were the same as those for ascorbic acid detection except that the ascorbic acid was replaced with an actual sample. The concentration of the above sample was diluted to within the linear detection range of ascorbic acid. Finally, the total antioxidant capacity in the sample is expressed in ascorbic acid/liter.
Thereby further exploring the utility of the method in the analysis of actual commercial samples. Based on CuNi/CoMoO 4 Better laccase-like activity, and the TAC sensor is developed by taking AA as an antioxidant model. TAC is an important comprehensive index for evaluating the antioxidant capacity of an actual sample and can be used as an antioxidant biomarker for monitoring the health of organisms. Therefore, the development of a sensitive TAC detection technology is of great significance. Here, five commercial beverages were selected as the analysis targets. The test result is basically consistent with the technical index of the actual sample, which shows that the method can meet the test requirement of the actual sample and has certain practical significance.
(III) CuNi/CoMoO 4 Examples of the catalytic degradation of phenolic contaminants
To test CuNi/CoMoO 4 The laccase activity of (a) utilizes different laccase substrates including hydroquinone, phenol, dichlorophen, parachlorophenol, ortho-nitrophenol, and ortho-aminophenol. First, 100. mu.L of 1mg/mL of uniformly dispersed CuNi/CoMoO 4 Adding 2- (N-morpholinyl) ethanesulfonic acid monohydrate with pH of 7.0, total volume of 1.5mL and concentration of 50mMAnd (MES) buffer solution, 100 mu L of different laccase substrates with the concentration of 1mg/mL and 100 mu L of 4-aminoantipyrine with the concentration of 1mg/mL are respectively added, and after incubation for 1.5h at 37 ℃, the absorbance of different laccase substrates is measured at 510nm by using an ultraviolet-visible spectrophotometer. For comparison, 100. mu.L of 1U/mg of the natural laccase was also investigated according to the same procedure. The results are shown in FIG. 9.
Due to CuNi/CoMoO 4 Has laccase-like activity, and can be used for degrading 2, 4-DP. Furthermore, to evaluate CuNi/CoMoO 4 Substrate universality of nano-enzyme, which is mixed with different types of phenol and color developing agent (4-AP), proves that CuNi/CoMoO 4 Not only can catalyze the oxidation of the phenolic substances, but also has catalytic activity equivalent to or slightly superior to laccase, which shows that CuNi/CoMoO 4 The nano enzyme has good substrate universality.
(IV) CuNi/CoMoO 4 Example of catalytic degradation applied to acid fuchsin
Evaluation of CuNi/CoMoO 4 Catalytic activity on Acid Fuchsin (AF) degradation. A simulated dye solution was prepared by adding acid fuchsin to distilled water at a concentration of 15 mg/L. Prior to measurement, 100. mu.L of 1.5mg/mL CuNi/CoMoO containing 10mL of an acid fuchsin solution (pH 5.0) and 400. mu.L of 2mg/mL Peroxosulfate (PMS) was prepared in a 25mL beaker 4 A mixed solution of the suspension, which is then uniformly dispersed with ultrasonic waves. The absorbance of the suspension at 545nm was recorded with a UV-Vis spectrophotometer for a predetermined period of time. The degradation efficiency of AF was calculated as follows:
eta: degradation efficiency;
C 0 : initial concentration of acid fuchsin (mol. L) -1 )；
C t : concentration of acid fuchsin at t (mol. L) -1 )
The activation of AF by PMS evaluated CuNi/CoMoO 4 The catalytic performance of (2). PMS and H 2 O 2 Having similar O-O bonds, can be made strongAn oxidizing agent. PMS and H 2 O 2 Standard oxidation/reduction potential (E) 0 ) 1.82V and 1.776V, respectively. However, they have a limited ability to independently oxidize organic substances. To solve this problem, CuNi/CoMoO is used 4 PMS is activated to obtain SO with stronger oxidation capacity 4 ·- And OH. Wherein the SO has a higher oxidation-reduction potential 4 ·- The degradation capability of (2.5-3.1V) to pollutants is stronger than that of OH (1.8-2.7V). As shown in fig. 10, PMS reduced AF by only 5.80% within 40min, indicating that PMS produced almost no active radicals without catalyst. Similarly, the degradation efficiency of a single catalyst for AF was about 58.36%, indicating that CuNi/CoMoO 4 Has excellent specific surface adsorption AF. But when CuNi/CoMoO 4 When PMS and AF coexist, the degradation efficiency of AF reaches 99.45 percent, which shows that CuNi/CoMoO 4 The PMS can be well activated to achieve efficient degradation of AF. In addition, the CuNi/CoMoO4 can still maintain a good structure after degrading AF, which indicates that the catalyst has strong stability.
CuNi/CoMoO was studied by a series of control experiments 4 Degradation performance for AF. First, the effect of the initial pH of AF on the degradation efficiency was investigated. As shown in fig. 11-12, the degradation efficiency of AF was above 80% in the range of 3.0-6.0, and the reaction rate constants were calculated for AF solutions at different pH values, here the first order rate constant (k) was calculated, reaching the highest k (0.18/min) at pH 5, consistent with the AF degradation results. However, when the pH was 5 or more, the removal rate showed a tendency of slightly decreasing due to HSO 5 - To be reacted with CuNi/CoMoO 4 The main substances of surface active center interaction, and H in PMS + And the strong hydrogen bond formed by the O-O bond inhibits the generation of free radicals. In addition, PMS undergoes self-decomposition at high pH, thereby reducing the generation of free radicals.
(V) CuNi/CoMoO 4 Examples of catalytic Oxidation for epinephrine
The following colorimetric reactions were performed under optimal conditions to measure epinephrine, with different concentrations of epinephrine injected into the solution containing 1mg/mLCuNi/CoMoO 4 Aqueous MES buffer (50mM, pH 7.0)Total volume 1.5 mL). The mixture was reacted at 37 ℃ for 1.5 h. Thereafter, the epinephrine oxidation product is measured by an ultraviolet spectrophotometer at 485 nm. For comparison, a solution of the natural laccase (1U/mg, 100. mu.L) was also investigated in the same manner.
To further explore CuNi/CoMoO 4 The application of the nano enzyme takes epinephrine as a model molecule. Natural laccase and CuNi/CoMoO 4 The nano enzyme has the capability of catalyzing epinephrine to form a colored oxidation product. Epinephrine and CuNi/CoMoO 4 The oxidation product generated by the reaction has a characteristic absorption peak at 485nm, and can be used for detecting epinephrine. As shown in FIG. 13, the absorbance was linearly related to the concentration of epinephrine (5 to 50. mu.g/mL) and the coefficient of measurement (R) 2 ) Is 0.997.
(VI) CuNi/CoMoO 4 Example of visual analysis for epinephrine
In order to conveniently measure epinephrine, a simple and inexpensive portable device based on a smart terminal was developed. Different concentrations of epinephrine were mixed with 1mg/mLCuNi/CoMoO 4 The reaction was mixed in MES buffer (total volume 1.5mL) at 37 ℃ for 1.5 h. The mixed solution (CuNi/CoMoO) is then mixed 4 Epinephrine) were transferred to glass test tubes, placed in black boxes and illuminated with fluorescent light. The colorimetric images are collected through an intelligent terminal camera system, and a plurality of regions of the obtained photos are selected and converted into R, G, B channel values through an artificial intelligence concentration analysis application program independently developed by the inventor of the invention. A standard curve for epinephrine response was fitted with APP based on R/G (R value divided by G value). And finally, the detection results of the linear equation and the correlation coefficient are displayed on a screen, so that a foundation is laid for quick visual detection and accurate detection of epinephrine by an intelligent terminal.
In order to meet the requirements of site visualization and convenient analysis. In this research, with visual colorimetric signal and intelligent terminal platform integration, carry out RGB analysis to the image, conveniently survey adrenalin. As shown in fig. 14, when a series of concentrations of epinephrine were added to the reaction system, images were collected by the smart terminal. Then, images are selected with a self-developed applicationThe obtained images are analyzed on line, R, G, B, R/G (R divided by G), R/B (R divided by B), G/B (G divided by B) and gray values are counted, R/G values and epinephrine concentration are selected to be subjected to linear fitting, a fitting curve is automatically generated after the intelligent terminal platform is analyzed, and Y is 0.7561+0.0344X (R is 0.7561+ 0.0344X) (R is divided by B) 2 0.9937). Therefore, a visual, intuitive and convenient method for detecting epinephrine in real time is established without expensive equipment.
The CuNi/CoMoO serving as the multifunctional laccase-like enzyme is prepared by the method 4 The preparation method and the application have the following technical effects:
(1) the CuNi/CoMoO is prepared by a method combining hydrothermal treatment, calcination and impregnation 4 The CuNi nano-particles increase the specific surface area of the composite material, expose more Cu (I) active centers, facilitate the adsorption of reactants to participate in enzyme catalytic reaction, and show better catalytic activity even under extreme pH, temperature, long-term storage and high salt concentration 4 Also shows higher activity.
(2) Using CuNi/CoMoO 4 The laccase-like enzyme activity establishes a colorimetric sensor of ascorbic acid, the linear range of the colorimetric sensor is 1-150 mu M, the detection limit is 0.70 mu M, and the detection limit and the linear range of the colorimetric sensor are equivalent to or even better than those of methods obtained by other sensors.
(3) Can effectively degrade phenolic pollutants and environmental pollutants, CuNi/CoMoO 4 Not only can catalyze the oxidation of phenolic substances, but also has catalytic activity equivalent to or slightly superior to laccase, and the catalytic activity shows that CuNi/CoMoO 4 The nano enzyme has good substrate universality.
(4) A portable intelligent terminal platform combined with a chrominance signal is constructed by taking epinephrine as a model of phenolic pollutants, and a visual, visual and convenient epinephrine instant detection method is established without expensive equipment.
(5)CuNi/CoMoO 4 Due to the catalytic generation of SO 4 ·- And OH, realizing efficient degradation of acid fuchsin.
Finally, it should be noted that: the above-mentioned embodiments are only used for illustrating the technical solution of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 The preparation method is characterized by comprising the following steps:
S1：CoMoO 4 preparation of
Mixing Na 2 MoO 4 ·2H 2 O and Co (NO) 3 ) 2 ·6H 2 Fully stirring and dissolving O in deionized water, and then reacting in a high-pressure kettle; after centrifugal separation, washing with deionized water and ethanol for three times to obtain a precursor; then vacuum drying is carried out, and the precursor is calcined to obtain the CoMoO 4 ；
S2：CuNi/CoMoO 4 Preparation of
Adding CuCl 2 ·2H 2 O、NiCl 2 ·6H 2 O and prepared CoMoO 4 Dissolving in deionized water and stirring; then adding NaHB 4 Stirring, washing with deionized water and ethanol, and vacuum drying to obtain CuNi/CoMoO 4 ；
Wherein:
in step S1:
Na 2 MoO 4 ·2H 2 o and Co (NO) 3 ) 2 ·6H 2 The dosage ratio of O is a molar ratio, and the molar ratio is 1: 1;
the reaction conditions in the autoclave were: the reaction temperature is 155-165 ℃, and the reaction time is 9-11 h;
the vacuum drying temperature is 75-85 ℃, the calcining temperature is 345-355 ℃, and the calcining time is 1.5-2.5 h;
in step S2:
CuCl 2 ·2H 2 o and NiCl 2 ·6H 2 The dosage ratio of O is a molar ratio which is 1-6: 1;
stirring in deionized water for 2-4 h;
NaHB 4 the concentration of (2) is 9-11mg/mL, NaHB is added 4 The later stirring time is 4-6 h;
the temperature of vacuum drying is 75-85 ℃.
2. CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 The method of claim 1, wherein the CuNi/CoMoO prepared by the method of claim 1 is used 4 Application to the determination of ascorbic acid:
uniformly dispersing CuNi/CoMoO 4 Adding into tris buffer solution, adding 2, 4-dichlorophenol, 4-aminoantipyrine and ascorbic acid with different concentrations, and incubating at 37 deg.C for 1.5h to obtain red sample;
then, measuring the absorbance of the reaction solution at 510nm by using an ultraviolet-visible spectrophotometer;
wherein the content of the first and second substances,
CuNi/CoMoO 4 the concentration of (3) is 1.0mg/mL, the pH of the tris hydrochloride buffer solution is 6.5, the concentration of 2, 4-dichlorophenol is 1mg/mL, and the concentration of 4-aminoantipyrine is 1 mg/mL.
3. The CuNi/CoMoO as a multifunctional laccase-like enzyme according to claim 2 4 The application of (2), which is characterized in that:
the linear detection range of the ascorbic acid is 1-150 mu M, and the detection limit is 0.70 mu M;
wherein:
when the linear detection range of the ascorbic acid is 1-50 mu M, the calibration curve is that Y is 0.04281X +0.05396, R 2 ＝0.98826；
When the linear detection range of the ascorbic acid is 51-150 mu M, the calibration curve is that Y is 0.00616X +1.69368, R 2 ＝0.99611；
Wherein: and X is the concentration of ascorbic acid.
4. CuNi/CoMoO serving as multifunctional laccase-like enzyme sample 4 The method of claim 1, wherein the CuNi/CoMoO prepared by the method of claim 1 is used 4 The method is applied to the catalytic degradation of phenolic pollutants:
uniformly dispersing CuNi/CoMoO 4 Adding the mixture into 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution, then respectively adding different laccase substrates and 4-aminoantipyrine, incubating for 1.5h at 37 ℃, and then measuring the absorbance of different laccase substrates at 510nm by using an ultraviolet-visible spectrophotometer;
the laccase substrate is benzenediol, phenol, dichlorophen, parachlorophenol, o-nitrophenol or o-aminophenol;
wherein the content of the first and second substances,
CuNi/CoMoO 4 the concentration of (a) is 1.0mg/mL, the pH of the 2- (N-morpholino) ethanesulfonic acid monohydrate buffer is 7.0, the concentration is 50mM, the concentration of the laccase substrate is 1mg/mL, and the concentration of the 4-aminoantipyrine is 1 mg/mL.
5. CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 The method of claim 1, wherein the CuNi/CoMoO prepared by the method of claim 1 is used 4 Application to the catalytic degradation of acid fuchsin:
preparing a mixed solution of CuNi/CoMoO4 suspension containing an acid fuchsin solution and peroxymonosulfate, uniformly dispersing the mixed solution by using ultrasonic waves, and measuring the absorbance of the suspension at 545nm by using an ultraviolet-visible spectrophotometer;
wherein the content of the first and second substances,
the pH of the acid fuchsin solution is 3.0-6.0, and the CuNi/CoMoO 4 The concentration of (2) is 1.5mg/mL and the concentration of peroxymonosulfate is 2 mg/mL.
6. CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 The method of claim 1, wherein the CuNi/CoMoO prepared by the method of claim 1 is used 4 Application to the catalytic oxidation of epinephrine:
infusing adrenaline with different concentrations into the capsuleWith CuNi/CoMoO 4 In 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution of the aqueous dispersion, the mixture is reacted for 1.5h at 37 ℃ for oxidation, and then the epinephrine oxidation product is measured at 485nm by an ultraviolet spectrophotometer;
wherein:
CuNi/CoMoO 4 the concentration of (A) is 1.0mg/mL, the pH of the 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution is 7.0, and the concentration is 50 mM;
the linear curve of epinephrine and absorbance is Y-0.01661X +0.12833, R 2 And (3) 0.99745, wherein X is the concentration of adrenaline, and the linear detection range of the adrenaline is 5-50 mu g/mL.
7. CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 The method is characterized in that the CuNi/CoMoO prepared by the preparation method of claim 1 is used as a visual detection platform based on a portable intelligent terminal 4 Visual assay applied to epinephrine:
different concentrations of epinephrine were mixed with CuNi/CoMoO 4 Mixing and reacting for 1.5h in 2- (N-morpholinyl) ethanesulfonic acid monohydrate buffer solution at 37 ℃; then adding CuNi/CoMoO 4 Transferring the epinephrine mixed solution into a glass test tube, placing the test tube in a black box and illuminating with a fluorescent lamp;
then, an intelligent terminal is used for collecting colorimetric images, multiple regions of the obtained photos are selected and converted into R, G, B channel values, APP is used for fitting a reaction standard curve of epinephrine according to R/G, and finally the detection results of a linear equation and a correlation coefficient are displayed on a screen;
wherein:
CuNi/CoMoO 4 the concentration of (2) - (N-morpholino) ethanesulfonic acid monohydrate buffer was 1.0mg/mL, and the pH was 7.0 and the concentration was 50 mM.
8. The CuNi/CoMoO as a multifunctional laccase-like enzyme according to claim 7 4 The application of (2), which is characterized in that:
the curve fitted for epinephrine is Y-0.7561 +0.0344X, R 2 ＝0.9937, X is the concentration of adrenaline, and the linear detection range of the adrenaline is 5-50 mug/mL.
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